Palladium/Amine Dual-Catalyzed Tsuji–Trost Fluoroallylation of Aldehydes with gem-Difluorinated Cyclopropanes

We herein disclose the Pd/amine dual-catalyzed ring-opening cross-coupling reaction between gem-difluorinated cyclopropanes (gem-F₂CPs) with aldehydes, which enables the diversity-oriented synthesis (DOS) of 2-fluoroallylic aldehydes bearing all-carbon quaternary centers with features of broad scope and excellent functional group tolerance. The synthetic value of this Tsuji-Trost system was further demonstrated by late-stage functionalization of natural product-derived gem-F₂CPs and the diverse synthesis of various fluoroallylic aldehyde derivatives, including alcohol, alkyne, alkene, and amine.